Process for the isolation of water-soluble vitamins



Patented May 1935 UNITED STATES PATENT OFFICE PROCESS FOR THE ISOLATIONWATER-SOLUBLE VITAMINS Richard J. Block, New York, N. Y., and George R.Cowgill, Hamden, Conn., assignors to Simon J. Dannenberg, New York, N.Y.

No Drawing. Application April 20;- 1932, Serial No. 606,514

. 6 Claims. (01. 167-81) v Our invention relates to the isolation ofvitadrogenperoxide are added and the solution co mins and refersparticularly to processes for the tinued at gentle boiling until nofurther water isolation of the water-soluble vitamins fromsub distillateis obtained. The precipitate salts are stances containing them. thenremoved by filtration and the solvents and Numerous attempts have beenmade. to sepaexcess acid are removed by concentration. P 5 rate thewater-soluble vitamins and especially er bly in vacuo- During thisprocess practically the antineuritic vitamin from substances cono t eundesirable substances are removed taining them, but these have provedineffectual s t Solution s b n C d from -q chiefly because of thepartial decomposition of 01 Solution to an eleOhOl SOhItiOnthe vitaminsduring the process or because the Exam 1e 2 10 finalproductcontained-deleterious plant or anip mal bases, amines, and otherimpurities which The Same as Example 1 except at 1 e. 0- rendered theproduct und sir bl f r, m. of fuming nitric acid are substituted for thepossible of, correct and safe injection. 125 c. c. of hyd Peroxide Wehave found, however, that oxidizing com- Exam 1e 3 '15 pounds, while notafiecting the quantity coni p tent of the antineuritic vitamin and otherwater- T Same as Example 1 except h grams mm vitamins, efiectivelydestroy these potassium bichromate are substituted for the purities, orconverts the carbohydrates of high 125 cc. of hydrogen peroxide.

molecular weights into acid, or acid-like,com- Exam le 4 20 pounds ofsmaller molecular weights, which latp I ter compounds do not afiect theefliciency, or The Same as E p 1 except that 31 g a safety, ofparenteral injections of the substances Potassium permanganate aresubstituted for the thus obtain d, 125 c. c. of hydrogen peroxide.

5 Inthe following of our process, we prefer to a e 5 employ a crudevitamin, concentrate prepared 5 from rice polish, yeast, wheat germs orother The Same as Example 1 e p t a t water-soluble vitamin-containingsubstances, bon tetrachloride is substituted by an equal and especiallythose containing antineuritic quantity of chloroform and the 125hydrovitamin. gen peroxide are substituted by 62 grams sodium-, 30

A suitable concentrate can be produced by ex-P-t0111ene-Si11ph0eh10remide m e' tracting the vita innt i i t t Inplace of the ethyl alcohol mentioned in water or dilute alcohol,concentrating or evapoe fi examples, We een'employ other 9100- rating todryness. hols, among which are n-propyl alcohol, isoa5 a We give thefollowing as examples of the folpropyl alcohol, ellyl alcohol, y a cohotertiary butyl alcohol and tertiary amyl alcohol E l 1 Instead of thementioned carbon tetrachloride camp 6 and chloroform, we can employother solvents A quantity of the above described crude vitawhich willProduce & ternie-ry b ilin p i m lowing of our process:

40, min concentrate solution containing about 30 time w an alcohol and wte 40 grams of total solid is acidified with concern A on e idizinproduct which w ha tratedhydrochloric acid. To this solution,we addfound Suitable employment in 0111 Process an excess of barium chlorideuntil no further are nitric acid, chromic acid, hydrogen peroxide,precipitate forms and. two 'volumes of 1 to 1 potassium perm chlemmine 1m extraction of ethyl alcohol and carbon tetrahyp o d d P m} eh t 45chloride, respectively, this mixture of ethyl al- In the foregoingexamples, we have indicated cohol and carbon tetrachloride having aterniary the oxidation during the step of treatment with boiling pointof about 61 C. which is lower than the alcohol-tetrachloride oralcohol-chloroform, the boiling point of either of these compounds. butthe oxidation can also be accomplished either 60 The solution is placedin a fractionating distillbefore or after this alcohol-solvent step ofing apparatus essentially the same as that deprocedure. scribedinOrganic Syntheses 1,68, 192 1-J. Wiley The operation can also beperformed in the 8; Sons, except that the mechanical stirrer is.presenceof water and alcohol, without a solvent replaced by a droppingf el. The solution is such as carbon tetrachloride or chloroform, a"heated to a gentle boiling and 125 c. c. of hybut in this process theproportion of alcohol to water must be maintained by the addition oflarge amounts oi absolute alcohol.

The addition of barium chloride may be omitted, but we prefer to employit as it appears 5 to prevent the formation of poisonous products.

a means for clearly describing the process of our invention.

What we claim is: 1. In a process for the isolation of watersolubleantineuritic vitamins from materials containing them, the steps whichconsist in oxidizing a terniary iling point and separating the vitaminsolution from the precipitated impuri- 25 ties.

3. In a process for the isolation or watersoluble antineuritic vitaminsfrom materials con them, the steps which consist in oxidizing theimpurities in the presence of an 4. In a process soluble antineuriticvitamins from materials containing them, the steps which consist inoxidizing the impurities in the presence of an organic solvent for thevitamins and barium chloride and separating the vitamin solution 10 fromthe preciptated impurities. V

5. In a process for the isolation of wateroluble antineuritic vitaminsfrom materials containing them, the steps which consist in oxidizing theimpurities in the presence of an alcohol-containing organic solvent forthe vitamins having a terniary boiling point and barium chloride andseparating the vitamin solution, from the precipitated impurities. v

6. In a process for the isolation of watersoluble antineuritic vitaminsfrom materials containing them, the steps which consist in oxidizing theimpurities in the presence of an organic solvent for the vitamins andbarium chloride, and separating the vitamin solution 25 from theprecipitated impurities.

RICHARD J. BLOCK. GEORGE R. COWGILL.

for the isolation of ,water- 5

